Aluminum(III) is inherently electron deficient and therefore acts as a prototypical Lewis acid. Conversely, Al(I) is a rare, nucleophilic variant of aluminum that is thermodynamically unstable under ambient conditions. While attempts to stabilize and isolate Al(I) species have become increasingly successful, the parent Al(I) (i.e, Al−H) remains accessible only under extreme temperatures/pressures or matrix conditions. Here, we report the isolation of the parent Al(I) hydride under ambient conditions via the reduction of a Lewis-base-stabilized alkyldihaloalane. Computational and spectroscopic analyses indicate that the ground-state electronic configuration of this monomeric aluminum species is best described as an Al(I) hydride with non-negligible open-shell Al(III) singlet diradical character. These findings are also supported by reactivity studies, which reveal both the p-centered lone pair donating ability and the hydridic nature of the parent aluminene.

Polyhedral metallocalixarene nanocage cluster based on pure Ti(IV) ion are to our knowledge un-known hitherto. Herein we reported the first Ti(IV)-based metallocalixarene nanocage cluster by assembling a [Ti13O14] cage with...

High-valence Ti(IV)-based metallocalixarene coordination cages that are linked by oriented ancillary ligands are unknown so far. Herein, the first family of tunable calixarene-based coordination cages of Ti(IV) with a framework...

Reactions between Rosenthal’s zirconocene synthon, [Cp2Zr­(py)­Me3SiCCSiMe3] (py = pyridine), and two different types of bis­(alkynyl) boranes, (Me3Si)2NB­(CCSiMe3)2 and MesB­(CCSiMe3)2 (Mes = 2,4,6-trimethylphenyl), both resulting in the formation of η5-coordinated bis­(alkynyl)­borane zirconocene complexes. X-ray diffraction analysis revealed their six-membered cyclic structures featuring a boat conformation with considerable Zr–B interactions. The Zr–B bonding strength and conformational lability of the ZrC4B ring are dependent on the π basicity of the exocyclic B substituent. These compounds represent the first examples of η5-coordinated acyclic boron-containing π ligands.

Two neutral super electron donors (SEDs) based on C–C single bond have been developed.